CN108886841A - heating element - Google Patents

heating element Download PDF

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Publication number
CN108886841A
CN108886841A CN201680084519.XA CN201680084519A CN108886841A CN 108886841 A CN108886841 A CN 108886841A CN 201680084519 A CN201680084519 A CN 201680084519A CN 108886841 A CN108886841 A CN 108886841A
Authority
CN
China
Prior art keywords
pattern
bonding film
film
heating element
conductive heater
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680084519.XA
Other languages
Chinese (zh)
Other versions
CN108886841B (en
Inventor
明志恩
金世罗
金姝延
林枪润
李承宪
宋文燮
李光珠
黄智泳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Corp
Original Assignee
LG Chemical Co Ltd
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Filing date
Publication date
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Publication of CN108886841A publication Critical patent/CN108886841A/en
Application granted granted Critical
Publication of CN108886841B publication Critical patent/CN108886841B/en
Active legal-status Critical Current
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/20Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/26Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/20Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/22Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible
    • H05B3/26Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base
    • H05B3/265Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater non-flexible heating conductor mounted on insulating base the insulating base being an inorganic material, e.g. ceramic
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/84Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/0201Thermal arrangements, e.g. for cooling, heating or preventing overheating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/013Heaters using resistive films or coatings
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2214/00Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
    • H05B2214/02Heaters specially designed for de-icing or protection against icing
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0306Inorganic insulating substrates, e.g. ceramic, glass
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/11Printed elements for providing electric connections to or between printed circuits

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Surface Heating Bodies (AREA)
  • Resistance Heating (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to a kind of heating element and its manufacturing methods, more specifically, providing a kind of heating element and its manufacturing method, the heating element include:Bonding film;And the conductive heater pattern on the bonding film is set, wherein relative to the adhesive strength before application outside stimulus, the bonding film due to outside stimulus there is at least 30% bonding force to reduce ratio.

Description

Heating element
Technical field
The South Korea patent application No.10-2016- submitted this application claims on 04 29th, 2016 in Korean Intellectual Property Office 0053158 priority and right, all the contents of the application are incorporated by reference into this specification.
Present specification describes a kind of heating element and its manufacturing methods.
Background technique
When automobile outwardly and inwardly between there are when the temperature difference, moisture or frost are formed on vehicle glass.It can use and add Hot glass solves the problems, such as this.Glass is heated using adherency heater wire sheet material on the glass surface to form heater wire or in glass Heater wire is formed directly on a surface, heat is generated by heater wire by applying electric power to the both ends of heater wire, and thus improve glass The principle of the temperature on glass surface.
Specifically, simultaneously there is the method for excellent optical property to be substantially divided into for providing heat to automobile front glass Two types.
First method is to form transparent conductive film on entire glass surface.Form the method packet of transparent conductive film The transparent conductive oxide film using such as ITO is included, or by forming thin metal layer and then above and below metal layer Method using transparent insulating film to increase transparency.The advantages of this method is that optically excellent conductive film can be formed, A disadvantage, however, is that calorific value appropriate cannot be obtained at low voltage due to relatively high resistance value.
Second method can be used using metal pattern or wire and the region by making no pattern or wire The method for maximizing to increase transparency.Typical products using this method include by by tungsten wire insertion be used to be bonded automobile before Manufactured heating glass in the PVB film of glass.In the method, the diameter of the tungsten wire used is 18 microns or more, and The electric conductivity that can ensure enough calorific values at low voltage can be obtained, however, disadvantage is since tungsten wire is relatively crude, tungsten wire It is visually clearly visible.In order to overcome the problem, metal pattern, Huo Zheke can be formed on a pet film by printing technology To form metal pattern by photoetching process later on metal layer to be attached to polyethylene terephthalate (PET) film. It is formed with the PET film of metal pattern by being inserted between two polyvinyl butyral (PVB) films, then carries out glass bonding Technique can prepare the heating product that can be heated.A disadvantage, however, is that by being inserted into PET film between two PVB films, by Refractive index difference between PET film and PVB film will lead to the object deformation seen by vehicle glass.
Summary of the invention
Technical problem
This specification is intended to provide a kind of heating element and its manufacturing method.
Technical solution
One embodiment of this specification provides a kind of heating element, including:Bonding film;And it is arranged in the bonding Conductive heater pattern on film, wherein based on the adhesive strength before outside stimulus, the bonding film has by outside stimulus 30% or more adhesive strength reduces.
Beneficial effect
According to embodiment described in this specification, conductive heater figure can be formed in the transparent substrates of final products Case, so that the transparent substrates for being used to form conductive heater pattern are not kept in final products.As described above, being used for by removing In addition the bonding film for forming conductive heater pattern, can not use in addition to adhesive film between two transparent substrates of final products Film in addition, and can prevent the visual field as caused by the refractive index difference between film from deforming.
Detailed description of the invention
Fig. 1 shows the structure of the heating element of the first embodiment according to this specification;
Fig. 2 shows the structures according to the heating element of second embodiment of this specification;
Fig. 3 shows the structure of the heating element of the third embodiment according to this specification;
Fig. 4 shows the image of the Examples 1 and 2 and comparative example 1 that measure using optical microscopy.
<Appended drawing reference>
100:Bonding film
200:Conductive heater pattern
300:Substrate
400:Darken pattern
Specific embodiment
Hereinafter, it will be described in detail this specification.
Heating element according to this specification embodiment includes:Bonding film;And it is arranged in the bonding film On conductive heater pattern.
This specification is related to a kind of metal pattern transfer membrane, by forming metal pattern in the controllable substrate of adhesive strength Then metal pattern is only transferred to another substrate by controlling adhesive strength, to pass through the metal for forming not substrate forms Pattern can improve optical property and simplify technique.
Bonding film is applying the front support metal film or metal pattern of outside stimulus, and needs no degumming (decoating) or defect, and later there is the adhesive strength reduced by outside stimulus and need to have good Metal pattern transfer performance.
When forming conductive heater pattern using etch process after forming metal film on bonding film, bonding film needs pair The stripping solution of the etching solution and release etch protection pattern that etch metal film has acid resistance and alkali resistance.Herein, it bonds The acid resistance and alkali resistance of film are visually observed after being immersed in etching solution or stripping solution by bonding film without passing through To color change, its all or part of be not accompanied by that dissolution is removed and whether bonding film with initial phase than keeps phase With adhesive strength level determine.
Bonding film specifically, is can be with passing through outside with the film of adhesive strength control by outside stimulus Stimulate the film of reduced adhesive strength.Based on the adhesive strength before outside stimulus, bonding film can have by outside stimulus 30% or more adhesive strength reduces, and specifically, based on the adhesive strength before outside stimulus, bonding film can by outside stimulus To have the adhesive strength more than or equal to 30% and less than or equal to 100% to reduce, more specifically, based on before outside stimulus Adhesive strength, bonding film can have more than or equal to 50% by outside stimulus and is less than or equal to 100% and more has It is greater than or equal to 70% sharply and the adhesive strength less than or equal to 100% reduces.
Outside stimulus can be one of heat, light irradiation, pressure and electric current or a variety of, and outside stimulus can be light Irradiation, and can be preferred that ultraviolet light irradiates.
Ultraviolet light irradiation can be carried out with the light in the ultraviolet wavelengths in the range of 200nm to 400nm.It is ultraviolet Line exposure dose can be greater than or equal to 200mJ/cm2And it is less than or equal to 1200mJ/cm2, and preferably greater than or equal to 200mJ/cm2And it is less than or equal to 600mJ/cm2
Bonding film can have the initial adhesion strength of 20 to 2000 (180 °, gf/25mm), and viscous by outside stimulus The adhesive strength for closing film can be reduced to 1 to 100 (180 °, gf/25mm).Herein, it is surveyed using 180 ° of disbonded test measurement methods Measure bonding film adhesive strength, specifically, at room temperature 180 ° angle and 300mm/s rate under conditions of measure.It is logical Cross and form metal film on bonding film, and by gains be cut into width be 25mm come prepare be used for measure sample, and Power (gf/25mm) of the measurement from metal film stripping bonding film.
The thickness of bonding film is not particularly limited, however, the thickness with bonding film reduces, adhesion efficiency is reduced.It is viscous The thickness for closing film can be greater than or equal to 5 μm and be less than or equal to 100 μm.
The composition for being used to form bonding film is not particularly limited, for example, the composition for bonding film may include Binder resin, initiator and crosslinking agent.
Crosslinking agent may include selected from isocyanate ester compound, aziridine class compound, epoxy compounds and One of metal-chelating species compound or a plurality of types of compounds.Relative to the binder resin of 100 parts by weight, for gluing The composition of polymeric composition may include the crosslinking agent of 0.1 parts by weight to 40 parts by weight.When the content of crosslinking agent is too low, bonding The cementability of film can be insufficient, and when the content of crosslinking agent is too high, and the viscous of bonding film cannot be substantially ensured before photocuring Close intensity.
To the specific example of initiator, there is no limit and can be used commonly known initiator.In addition, relative to The binder resin of 100 parts by weight, the composition for bonding film may include the initiator of 0.1 parts by weight to 20 parts by weight.
Binder resin may include (methyl) acrylic resin that weight average molecular weight is 400,000 to 2,000,000.
In the present specification, (methyl) acrylate refers to including both acrylate and methacrylate.(methyl) The example of acrylic resin may include the copolymerization of (methyl) acrylic ester monomer and the monomer containing crosslinking functionality Object.
(methyl) acrylic ester monomer is not particularly limited, and the example may include (methyl) acrylic acid alkyl Ester, more specifically, may include, as the monomer of the alkyl with 1 to 12 carbon atom, (methyl) amyl acrylate, (first Base) n-butyl acrylate, (methyl) ethyl acrylate, (methyl) methyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) propylene Sour n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) dodecylacrylate and One of (methyl) decyl acrylate, two or more seed types.
Monomer containing crosslinking functionality is not particularly limited, and the example may include the monomer containing hydroxyl, One of monomer containing carboxyl and the monomer containing nitrogen, two or more seed types.
The example of compound containing hydroxyl may include (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl Base propyl ester, (methyl) acrylic acid 4- hydroxybutyl, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 2- hydroxyl glycol ester, (methyl) acrylic acid 2- hydroxyl propylene glycol ester etc..
The example of compound containing carboxyl may include (methyl) acrylic acid, 2- (methyl) acryloxyacetic acid, 3- (methyl) acryloxy propionic, 4- (methyl) acryloxy butyric acid, acrylic acid dimer, itaconic acid, maleic acid, maleic acid Acid anhydride etc..
The example of monomer containing nitrogen may include (methyl) acrylonitrile, n-vinyl pyrrolidone, N- vinyl in oneself Amide etc..
In addition (methyl) acrylic resin can be total in terms of other functions of enhancing such as compatibility At least one of polyvinyl acetate, styrene and acrylonitrile.
Composition for bonding film can also include ultraviolet-curing compound.To ultraviolet-curing compound Type is not particularly limited, also, it is, for example, possible to use the polyfunctional compounds that weight average molecular weight is 500 to 300,000.This Field those of ordinary skill can be readily selected suitable compound according to target application.Ultraviolet-curing compound can be with Including the polyfunctional compound with two or more ethylenically unsaturated double bonds.
Relative to the above-mentioned binder resin of 100 parts by weight, the content of ultraviolet-curing compound can be for 1 parts by weight extremely 400 parts by weight, and preferably 5 parts by weight are to 200 parts by weight.
When the content of ultraviolet-curing compound is less than 1 parts by weight, the adhesive strength after solidification reduces deficiency, causes The worry of transfer performance is reduced, and content is greater than 400 parts by weight and can cause the cementability of the preceding adhesive of ultraviolet light irradiation may The worry that meeting is insufficient or the removing with release film etc. may be not easily accomplished.
Ultraviolet-curing compound can also be bonded to (methyl) acrylic copolymer of binder resin with carbon-to-carbon double bond Side chain or main chain terminal form and add-on type ultraviolet-curing compound use.In other words, by can by ultraviolet light Curing compound is introduced into the monomer for polymerizeing (methyl) acrylic copolymer as binder resin, for example, (methyl) In acrylic ester monomer and monomer containing crosslinking functionality, or by make ultraviolet-curing compound in addition with polymerize The reaction of (methyl) acrylic copolymer, ultraviolet-curing compound can be introduced into (methyl) third as binder resin In the side chain of olefin(e) acid analog copolymer.
The type of ultraviolet-curing compound is not particularly limited, as long as its each molecule is comprising 1 to 5 and preferred 1 or 2 ethylenically unsaturated double bond, and have can with include in (methyl) acrylic copolymer as binder resin Crosslinking functionality reaction functional group.Herein, can in (methyl) acrylic copolymer as binder resin The example of the functional group for the crosslinking functionality reaction for including may include isocyanate group, epoxy group etc., and but not limited to this.
The specific example of ultraviolet-curing compound may include one of following, two or more seed types:Make For the substance comprising the functional group that can be reacted with the hydroxyl of binder resin, (methyl) acryloxy isocyanate, (methyl) Acryloyloxymethyl isocyanates, 2- (methyl) acryloyloxyethyl isocyanate, 3- (methyl) acryloxypropyl Isocyanates, 4- (methyl) acryloxy butyl isocyanate, acrylic-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methyl Propenoyl isocyanate or allyl iso cyanurate;
By reacting diisocyanate cpd or polyisocyanate compound with (methyl) acrylic acid 2- hydroxyl ethyl ester The acryloyl group monoisocyanate compound arrived;
By making diisocyanate cpd or polyisocyanate compound, polyol compound and (methyl) acrylic acid 2- The acryloyl group monoisocyanate compound that hydroxyl ethyl ester is reacted;Or
As the substance of the functional group comprising that can be reacted with the carboxyl of binder resin, (methyl) glycidyl Ester, allyl glycidyl ether etc., however, the ultraviolet-curing compound is without being limited thereto.
By replacing the crosslinking functionality of 5 moles of % to 90 moles of % in binder resin, ultraviolet-curing compound can To be included in the side chain of binder resin.When substitution amount is less than 5 moles of %, the drop of peel strength caused by being irradiated by ultraviolet light It is low to may be insufficient, and when substitution amount is greater than 90 moles of %, the cementability of the adhesive before ultraviolet light irradiation may drop It is low.
Composition for bonding film can suitably include tackifier, such as rosin resin, terpene resin, phenolic aldehyde tree Rouge, styrene resin, aliphatic petroleum resin, aromatic petroleum resin or the Petropols of aliphatic aromatic copolymerization.
The method that bonding film is formed on the substrate is not particularly limited, it is, for example, possible to use by by the use of the disclosure It is coated directly onto substrate in the composition of bonding film and forms the method for bonding film, be coated be used in separable substrate first Then bonding film is transferred in substrate the method etc. for preparing bonding film using separable substrate by the composition of bonding film.
The method of coating and the dry composition for bonding film is not particularly limited, it is, for example, possible to use such as lower sections Method:Using any means known such as chipping wheel coater, gravure coater, die coater or reversed coating machine, in the form of original or To dissolve the composition that form coating in a suitable organic solvent includes each component, and in 60 DEG C to 200 DEG C of temperature By solvent seasoning 10 seconds to 30 minutes under degree.In addition, in the above-mentioned methods, aging technique can be additionally carried out sufficiently to be glued The cross-linking reaction of mixture.
Substrate plays the role of supporting bonding film, and can remove together with bonding film when removing bonding film.
The material of substrate is not particularly limited, as long as it can play the role of supporting bonding film, for example, substrate It can be substrate of glass or flexible substrates.Specifically, flexible substrates can be plastic-substrates or plastic foil.
Plastic-substrates or plastic foil are not particularly limited, and the example may include polyacrylate, polypropylene (PP), polyethylene terephthalate (PET), polyvinylether phthalic acid ester (polyethylene ether Phthalate), polyethylene glycol phthalate, poly- phthalic acid butanediol ester, polyethylene naphthalate (PEN), Polycarbonate (PC), polystyrene (PS), polyetherimide, polyether sulfone, dimethyl silicone polymer (PDMS), polyether-ether-ketone (PEEK) and any one or more of polyimides (PI).
The advantages of flexible membrane substrate, is that bonding film or the bonding film for being provided with conductive heater pattern can be wound into a roll simultaneously Storage, for use in roll-to-roll processes.
The thickness of substrate is not particularly limited, specifically, 20 μm can be greater than or equal to and be less than or equal to 250 μm.
In the bonding film formed by the composition for bonding film, binder resin, crosslinking agent and ultraviolet-curing Close some functional groups bonding in object, to keep maintaining the smallest mechanical strength of the film, however, functional group have it is remaining so as to Carry out additional reaction.When applying the outside stimulus for reducing the adhesive strength of bonding film, by the residue of initiator initiation Functional group forms additional crosslinking, as a result, bonding film is hardened, and reduces adhesive strength.
The line height of conductive heater pattern can be 10 μm or less.Line height greater than 10 μm conductive heater pattern have by The shortcomings that light in the side surface of metal pattern reflects and increases metal identification.It is conductive according to the disclosure embodiment The line height of heating pattern is in the range of being greater than or equal to 0.3 μm and being less than or equal to 10 μm.According to the disclosure reality Scheme is applied, the line height of conductive heater pattern is in the range of being greater than or equal to 0.5 μm and being less than or equal to 5 μm.
In the present specification, the line height of conductive heater pattern refers to from the surface adjacent with bonding film to corresponding thereto The distance on surface.
According to the disclosure embodiment, conductive heater pattern is below with 20% or less and preferably 10% Line height tolerance.Herein, deviation refers to percentage of the difference based on average line height between average line height and each line height Than.
Conductive heater pattern can be formed by Heat Conduction Material.For example, conductive heater pattern can be formed by metal wire.Specifically Ground, heating pattern preferably include the metal for the thermal conductivity for having excellent.Heating pattern material advantageously has micro- more than or equal to 1 Ohmcm and the resistivity value for being less than or equal to 200 micro-ohm cms.The specific example of heating pattern material may include copper, Silver, aluminium etc..As conductive heater pattern material, copper most preferably cheap and with superior electrical conductivity.
Conductive heater pattern may include the pattern of the metal wire formed by straight line, curve, zigzag or their combination. Conductive heater pattern may include regular pattern, irregular pattern or their combination.
Total aperture opening ratio of conductive heater pattern, that is, be not preferably by the ratio for the basal region that conductive heater pattern covers 90% or more.
The line width of conductive heater pattern is 40 μm hereinafter, in particular 0.1 μm to 40 μm.Conductive heater pattern has 50 μm To the line line spacing of 30mm.
As shown in fig. 1, heating element may include bonding film 100;And the conductive heater pattern on bonding film 100 200.Herein, in conductive heater pattern 200, line height is h, and line line spacing is p, line width w.
Then conductive heater pattern can make metal film figure by forming metal film at least one surface of bonding film Case is formed, or can be transferred on bonding film by the metal pattern that will be patterned into be formed.
The methods of deposition, plating, metal foil laminated can be used to be formed in metal film, and conductive heater pattern can lead to Cross and form etching protection pattern on metal film using photoetching, ink-jet method, plate print process, roller printing method etc., then etch not by Etching protects the metal film of pattern covering to be formed.
Conductive heater pattern can be transferred on bonding film to be formed by the metal pattern that directly will be patterned into.Herein, Patterned metal pattern can be used lamination and be provided with metal foil or the roller printing method of metal pattern to be formed.
It can also include protective film according to the heating element of the another embodiment of the disclosure, protective film setting is bonding Film is provided on the surface of conductive heater pattern.Specifically, according to the needs in process aspect or according in final application Purposes, in the case where non-cohesive transparent substrates, can move when the face protective film to be removed (or release film) in the post-attachment or Handle heating element.It as the type of protective film, can be used those of known in the art, and the example may include plastics Film, the plastic foil for being coated with separated type material, paper, the paper for being coated with separated type material or the film of embossed surface processing.
The heating element that protective film is provided on the surface for being provided with conductive heater pattern of bonding film can wound Storage, mobile or processing when coiled.
It can also include darkening pattern according to the heating element of this specification embodiment, darkening pattern setting On conductive heater pattern or at least one of between conductive heater pattern and bonding film.
Darkening pattern can be set in region corresponding with conductive heater pattern, be particularly provided at conductive heater On the upper surface and/or lower surface of pattern, and can be set at least part of the side surface of conductive heater pattern with And in upper and lower surfaces, and it can be set on the entire upper surface, lower surface and side surface of conductive heater pattern.
In the present specification, pattern is darkened by being arranged on the upper surface and/or lower surface of conductive heater pattern, it can be with Reduce the visibility of the dependence reflectivity of conductive heater pattern.
In the present specification, darkening pattern can pattern together with conductive heater pattern or separately, still, independently form It is used to form the layer of each pattern.However, being present in accurate corresponding table each other to make conductive heater pattern and darken pattern On face, conductive pattern and darkening pattern are most preferably formed simultaneously.
In the present specification, it darkens pattern and conductive heater pattern is different from least some light absorbing materials and is embedded in or disperses To the structure in conductive heater pattern, or different from a part surface treatment physics for passing through single conductive layer of surface side Or the structure of chemical modification, because individually pattern layer forms laminar structure.
In addition, in the present specification, darken pattern be set up directly on bonding film or be set up directly on conductive pattern and It is not inserted into other adhesive layer or adhesive layer.
Single layer can be formed as by darkening pattern, or can be formed as the multilayer of two or more layers.
Darken the color that pattern is preferably close to netrual colour series.However, darkening pattern is not necessarily netrual colour, and even if When with color, it can also be introduced when with antiradar reflectivity.Herein, the color of netrual colour series refer to when for it is each at The wavelength divided, the color that the light into body surface is equably reflected and occurred when absorbing without selectively being absorbed. In the present specification, as pattern is darkened, can be used visibility region (when measurement total reflection in 400nm to 800nm) for Each wave-length coverage has the material of 50% or less total reflection standard deviation.
As darken pattern material it is preferable to use the black with above-mentioned physical property when forming front surface layer Dyestuff, black pigment, metal, metal oxide, metal nitride or metal oxynitride are as light absorbing material without spy It does not limit.For example, darken pattern can be used the composition comprising black dyes or black pigment by photoetching process, ink-jet method, Print process, roller printing method etc. carry out shape, or can under sedimentary condition that those skilled in the art set etc. by use Ni, Oxidation film, nitride film, oxide-nitride film, carbide membrane, metal film or the their combination of the formation such as Mo, Ti, Cr It is patterned to be formed.
Darken the pattern form for the line width that preferably there is pattern line width to be equal to or more than conductive heater pattern.
It, can in user's viewing when darkening the pattern form for the line width that there is pattern line width to be greater than conductive heater pattern Larger to provide the effect for darkening pattern screening conductive heating pattern, this causes effectively to block the light by conductive pattern itself The advantages of being influenced caused by pool or reflection.However, even if when darkening pattern has line width identical with conductive pattern, it can also be with Realize the target effect of this specification.
According to the heating element of this specification embodiment can also include substrate, the substrate setting with bonding On the opposite surface in the surface for being provided with conductive heater pattern of film.
Substrate plays the role of supporting bonding film, and can remove together with bonding film when removing bonding film.
The material of substrate is not particularly limited, as long as it can play the role of supporting bonding film, for example, substrate It can be substrate of glass or flexible substrates.Specifically, flexible substrates can be plastic-substrates or plastic foil.To plastic-substrates or modeling Material film is not particularly limited, and the example may include polyacrylate, polypropylene (PP), polyethylene terephthalate (PET), polyvinylether phthalic acid ester, polyethylene glycol phthalate, poly- phthalic acid butanediol ester, poly- naphthalene diformazan Sour glycol ester (PEN), polycarbonate (PC), polystyrene (PS), polyetherimide, polyether sulfone, dimethyl silicone polymer (PDMS), any one or more in polyether-ether-ketone (PEEK) and polyimides (PI).
The advantages of substrate is flexible membrane is that bonding film or the bonding film for being provided with conductive heater pattern can be wound into a roll And store, for use in roll-to-roll processes.
The thickness of substrate is not particularly limited, specifically, 20 μm can be greater than or equal to and be less than or equal to 250 μm.
Heating element can also include the busbar that the both ends of conductive heater pattern are arranged in.In addition, heating element may be used also To include the power supply unit for being connected to busbar.
According to the another embodiment of the disclosure, black pattern can be set with hidden bus bar.For example, black pattern can It is printed with using the paste containing cobalt oxide.Herein, silk-screen printing is suitable as printing process, and thickness can be set as 10 μm to 100 μm.Conductive heater pattern and busbar can be formed before or after each comfortable formation black pattern.
In lamination adhesive layer on the surface for being provided with conductive heater pattern of bonding film, it can store, move or handle Heating element.Specifically, the heating element of lamination adhesive layer can be on the surface for being provided with conductive heater pattern of bonding film It is stored, moves or handles when being wound into a roll.Herein, opposite with the surface for being provided with conductive heater pattern of adhesive layer On surface, the protective film to be removed (or release film) below may further include, and heating element can in this state With when being wound into a roll by storage, movement or processing.
Conductive heater when lamination adhesive layer on the surface for being provided with conductive heater pattern in bonding film, on bonding film Pattern can be embedded in adhesive layer side.Specifically, the conductive heater in the region with conductive heater pattern is completely covered in adhesive layer Pattern, and it is bonded to bonding film in the region of no conductive heater pattern, and the conductive heater pattern on bonding film can To be sealed by adhesive layer, so that almost without gap between the bonding film and adhesive layer for being provided with conductive heater pattern.
It, can be by before being laminated when lamination adhesive layer on the surface for being provided with conductive heater pattern in bonding film Applying to bonding film outside stimulus and reduces adhesive strength, and only conductive heater pattern is transferred on adhesive layer, or can be with Adhesive strength by reducing bonding film after laminate adhesive film and adhesive layer only shifts heating pattern.It is being transferred to adhesive layer On conductive heater pattern contacted with busbar after, gains are laminated to manufacture heating element together with transparent substrates.
After lamination adhesive layer on the surface for being provided with conductive heater pattern in bonding film, bonding film and only is removed When heating pattern is transferred on adhesive layer, when conductive heater pattern is embedded into adhesive layer side heating element can be stored, Mobile or processing.On at least one surface for being provided with the adhesive layer of conductive heater pattern, it may further include and want below The protective film (or release film) of removing, and in this state heating element can when being wound into a roll by storage, movement or Processing.
When being laminated transparent substrates on the surface for being provided with conductive heater pattern in bonding film, by before being laminated or Outside stimulus is applied to bonding film to reduce adhesive strength later, and by removing debonding after being laminated to transparent substrates Film, only conductive heater pattern can be transferred in transparent substrates.
Transparent substrates refer to the transparent substrates of the final products using heating element, for example, transparent substrates can be glass Substrate, and preferably can be vehicle glass.
According to embodiment described in this specification, conductive heater pattern can be formed in the transparent substrates of final products On, so that the transparent substrates for being used to form conductive heater pattern are not kept in final products.As described above, by removing debonding In addition film can not use between two transparent substrates of final products in addition to the transparent substrates for being bonded final products Film except adhesive film, and can prevent the visual field as caused by the refractive index difference between film from deforming.
It may be coupled to power supply for heating according to the heating element of the disclosure, and herein, calorific value can be 100W To the every m of 1000W2And the every m of preferably 200W to 700W2.Even if according to the heating element of the disclosure in low-voltage, such as 30V Or it is lower, preferably 20V or lower also there are excellent heating properties therefore can be used in automobile etc..Electricity in heating element Resistance is for 2 ohm-sqs hereinafter, preferably 1 ohm-sq is hereinafter, below more preferably 0.5 ohm-sq.The electricity obtained herein Resistance value has meaning identical with sheet resistance.
According to the another embodiment of the disclosure, heating element can be the heating element for vehicle glass.
According to the another embodiment of the disclosure, heating element can be the heating element for automobile front glass.
Hereinafter, this specification is more fully described in reference implementation example.However, what following embodiment was merely to illustrate Purpose, and it is not intended to limitation this specification.
[embodiment]
[embodiment 1]
The preparation of (methyl) acrylic resin
To reflux nitrogen and install in reactor of the cooling device to be easy to control temperature be added by 98.5 parts by weight The monomer mixture that 2-EHA (2-EHA) and the hydroxy-ethyl acrylate (HEA) of 13.5 parts by weight are formed.Then, Based on the monomer mixture of 100 parts by weight, be added 400ppm as chain-transferring agent (CTA) n-dodecyl mercaptan (n-DDM), With the solvent ethyl acetate (EAc) of 100 parts by weight, at 30 DEG C by gains be sufficiently mixed 30 minutes or longer time, simultaneously Nitrogen is injected to remove the oxygen of inside reactor.Later, it increases temperature and is maintained at 62 DEG C, thereto with the concentration of 300ppm Reaction initiator V-60 (azodiisobutyronitrile) is added with initiation reaction, by polymerizeing 6 hours the first reactants of preparation.
Mixed into the first reactant 15.3 parts by weight isocyanic acid 2- methacryloyloxyethyl (MOI) (relative to HEA in first reactant is 80 moles of %) and the 1 weight % relative to MOI catalyst (dibutyl tin dilaurate: DBTDL), gains react 24 hours at 40 DEG C, pass through the polymerization introducing ultraviolet curing group in the first reactant In object side chain, to prepare (methyl) acrylic polymer resin.
The preparation of bonding film
By by toluene di-isocyanate(TDI) (TDI) the kind isocyanate crosslinking agent of 3g and the initiator (Irgacure of 4g 184) it is mixed into (methyl) acrylic polymer resin of the upper surface of 100g preparation and prepares binding compositions.It will bonding Composition is coated on the PET with a thickness of 38 μm of release processing, and gains are dried 3 minutes at 110 DEG C to prepare thickness The bonding film that degree is 10 μm.The bonding film of formation is laminated on 150 μm of PET substrate's film, then Gains are subjected to aging to prepare bonding film.
The manufacture of heating element
After depositing 2 μm of Cu on bonding film using electron-beam evaporator, using reversed offset print technology in copper It is formed on film making etching protection pattern made of novolac resin as main component.It is in addition dried 5 minutes at 100 DEG C Afterwards, the copper in expose portion is etched by etch process, as a result, copper pattern is formed on bonding film.Herein, the copper pattern of formation Line width be 11 μm to 12 μm.
[embodiment 2]
After depositing 2 μm of Cu on the bonding film prepared in embodiment 1 using electron-beam evaporator, photoetching process is used Form etching protection pattern.Specifically, ink film is formed using photoresist ink on copper film by rotary coating, and Dry gains protect pattern to form etching in 5 minutes at about 100 DEG C.Dry sample is placed in lithographic equipment and uses mesh Then the mask exposure for case of marking on a map removes the ink in the part for being masked and shielding and be not exposed to light using stripping solution Film.After etching the copper in expose portion by etch process, ink is removed totally to form copper pattern.Herein, it is formed Copper pattern line width be 12 μm to 13 μm.
[comparative example 1]
After depositing 2 μm of Cu on conventional binder film using electron-beam evaporator, reversed offset print technology is used It is formed on copper film and protects pattern by making the etching that novolac resin as main component forms.It is in addition dried at 100 DEG C Gains etch the copper in expose portion after five minutes, by etch process, as a result, copper pattern is formed on bonding film.Herein, The line width of the copper pattern of formation is 12 μm to 13 μm.
[experimental example 1]
Result using the copper pattern prepared in optical microphotograph sem observation Examples 1 and 2 and comparative example 1 is shown in Figure 4.
Pass through Fig. 4, it may be determined that can preparation line height be 10 μm of metal patterns below on bonding film.
[experimental example 2]
There is the bonding film of conductive heater pattern using the formation prepared in embodiment 1, using heat-laminator to adhesive film (PVB) be bonded with conductive heater pattern, and by outside stimulus (ultraviolet light) change bonding film adhesive strength it Afterwards, bonding film is removed.
Utilizing the conductive heater formed on the conventional binder film prepared in comparative example 1 pattern bonded using heat-laminator After on to adhesive film (PVB), bonding film is removed.
The conductive heater pattern transfer performance of embodiment 1 and comparative example 2 is compared.As a result as shown in table 1.
[table 1]
Embodiment 1 Comparative example 1
Pattern transfer performance x
Pattern transfer performance refers to the property that the conductive heater pattern formed on bonding film is transferred on adhesive film (PVB) Energy.
O:Conductive heater pattern 100% is transferred on adhesive film, and with state identical with original state transfer without producing Raw pattern disconnects and fold
×:Conductive heater pattern is not transferred on adhesive film, and cannot act as heating film due to generating pattern disconnection.

Claims (7)

1. a kind of heating element, including:
Bonding film;And
Conductive heater pattern on the bonding film is set,
Wherein, based on the adhesive strength before outside stimulus, the bonding film has 30% or more bonding by outside stimulus Strength reduction.
2. heating element according to claim 1, wherein the outside stimulus is in heat, light irradiation, pressure and electric current It is one or more.
3. heating element according to claim 1, wherein the outside stimulus is ultraviolet light irradiation.
4. heating element according to claim 1, wherein the bonding film use includes binder resin, initiator and friendship Join the composition for bonding film of agent to prepare.
5. heating element according to claim 1 further includes substrate, being provided with for the bonding film is arranged in the substrate On the opposite surface in the surface of conductive heater pattern.
6. heating element according to claim 1 further includes darkening pattern, the darkening pattern setting adds in the conduction On thermal image at least one of between the conductive heater pattern and the bonding film.
7. heating element according to claim 1, wherein the line height of the conductive heater pattern is 10 μm or less.
CN201680084519.XA 2016-04-29 2016-12-23 Heating element Active CN108886841B (en)

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